Substituted oxazolidines and thiazolidines

ABSTRACT

Substituted oxazolidines and thiazolidines having the formula ##STR1## in which X is oxygen or sulfur; R is haloalkyl, alkyl or alkylthio; and R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are independently selected from the group consisting of hydrogen, lower alkyl, alkoxyalkyl and lower alkylol; provided that when X is oxygen and R is alkyl, then at least one of R 1 , R 2 , R 3 , R 4 , R 5  or R 6  is other than hydrogen. The compounds are active as an antidote against crop injury, when used with various herbicides.

This is a division, of application Ser. No. 655,938, filed Feb. 6, 1976, now U.S. Pat. No. 4,186,130, that application is a continuation-in-part of copending application Ser. No. 484,514, filed July 1, 1974, abandoned which in turn is a continuation of then copending application Ser. No. 356,548, filed May 2, 1973, now abandoned, which in turn is a continuation-in-part of then copending application Ser. No. 297,582, filed Oct. 13, 1972, now abandoned.

This invention relates to certain novel substituted oxazolidines and thiazolidines which are useful as antidotes against crop injury by various herbicides. The compounds of the present invention are new compositions of matter and correspond to the general formula ##STR2## in which X is oxygen or sulfur; R is haloalkyl, alkyl or alkylthio; and R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of hydrogen, lower alkyl, alkoxyalkyl and lower alkylol; provided that when X is oxygen and R is alkyl, then at least one of R₁, R₂, R₃, R₄, R₅ or R₆ is other than hydrogen.

In the above description, the following embodiments are intended for the various substituent groups: For R, haloalkyl and alkyl preferably includes, unless otherwise provided for, those members which contain from 1 to 10 carbon atoms, inclusive, in both straight chain and branched chain configurations, and the term halo includes chloro and bromo as mono, di, tri, tetra and per substitutions. As exemplary of the alkyl portion within the preferred embodiment are the following: Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, 1,1-dimethylbutyl, amyl, isoamyl, 2,4,4-trimethylpentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, nonyl, and decyl. The term alkylthio preferably includes those members which contain from 1 to 4 carbon atoms, inclusive, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, t-butylthio, and the like. For R₁, R₂, R₃, R₄, R₅ and R₆, the term lower alkyl preferably includes, unless otherwise provided for, those members which contain from 1 to 4 carbon atoms, inclusive, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, and the like. The term alkoxyalkyl preferably includes those members having a total of 2 to 4 carbon atoms, inclusive, for example, methoxymethyl, methoxyethyl, ethoxyethyl, ethoxymethyl and the like. The term lower alkylol preferably includes those members having 1 to 4 carbon atoms, inclusive, for example, methylol, ethylol, propylol and butylol.

PREFERRED EMBODIMENTS OF THE INVENTION

The preferred embodiments of the invention are realized when the following substitutions are present in compounds corresponding to the general formula (I), supra. ##STR3## in which X is oxygen, R is selected from the group dichloromethyl, tribromomethyl, trichloromethyl, 1-bromoethyl, monobromomethyl, 1,2,4,4-tetrabromopentyl, 2-chloroethyl, 1,2-dibromoethyl, 2-bromoethyl, ω-bromodecyl, 3-chloropropyl, 2-chloropropyl, 1-bromopropyl, 1-bromobutyl, 5-bromopentyl; R₁ is methyl, R₂ is selected from the group methyl, ethyl, t-butyl, i-propyl; R₃, R₄, R₅ and R₆ are each hydrogen; provided that when R is dichloromethyl, R₂ is other than methyl; in which X is oxygen, R is monochloromethyl, R₂ is selected from the group methyl, ethyl, t-butyl, i-propyl; and R₃, R₄, R₅ and R₆ are each hydrogen; ##STR4## in which R is haloalkyl having 1 to 10 carbon atoms, inclusive, and halo is selected from chloro and bromo, R₁ is lower alkyl having from 1 to 4 carbon atoms, inclusive, R₂ is lower alkyl having from 1 to 4 carbon atoms, inclusive, and R₃, R₄, R₅ and R₆ are each hydrogen; ##STR5## in which R is selected from the group tribromomethyl, monochloromethyl, dichloromethyl, 1-bromoethyl, monobromomethyl, 1,2-dibromoethyl, 2-chloropropyl, 1-bromopropyl, 1-bromobutyl, 3-chloropropyl, 5-bromopentyl; R₁ is methyl, R₂ is methyl, R₅ is methyl and R₃, R₄ and R₆ are each hydrogen; ##STR6## in which R is selected from the group consisting of dichloromethyl, trichloromethyl, monobromomethyl, 1-bromoethyl and tribromomethyl, R₁ is methyl, R₂ is methyl, R₃ is methyl and R₄ is methyl, and R₅ and R₆ are each hydrogen; ##STR7## in which R is haloalkyl having 1 to 10 carbon atoms, inclusive, halo is selected from chloro and bromo, R₁ is lower alkyl having 1 to 4 carbon atoms, inclusive, R₅ is lower alkyl having from 1 to 4 carbon atoms, inclusive, and R₂, R₃, R₄ and R₆ are each hydrogen; ##STR8## in which R is haloalkyl having from 1 to 10 carbon atoms, inclusive, halo is selected from chloro and bromo, R₃ is lower alkyl having from 1 to 4 carbon atoms, inclusive, and R₁, R₂, R₄, R₅ and R₆ are each hydrogen.

(8) Also, N-haloacyl (2-alkylated) oxazolidine wherein the haloacyl group is C₂₋₄ acyl, and the 4 and 5 carbon atoms of the oxazolidine ring are satisfied by hydrogen or C₁₋₆ alkyl groups.

Some of the compounds of this invention are active herbicides and can be used in herbicidal compositions to control the growth of undesirable vegetation. The compounds also are useful in plant growth regulating compositions, nematocidal, algicidal, bacteriostatic and fungicidal compositions.

Among the many herbicidal compounds commercially available, the thiocarbamates, alone or admixed with other herbicides such as the triazines, have reached a relatively high degree of commercial success. These herbicides are immediately toxic to a large number of weed pests at different concentrations varying with the resistance of the weed pests. Some examples of these compounds are described and claimed in the U.S. Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314.

It has been found in practice that the use of these thiocarbamates as herbicides on crops sometimes causes serious injuries to the crop plants. When used in the recommended amounts in the soil to control many broadleaf weeds and grasses, serious malformation and stunting of the crop plants result. This abnormal growth in the crop plants results in loss of crop yield. Previous attempts to overcome this problem involves the treatment of the crop seed with certain antagonistic agents prior to planting, see U.S. Pat. Nos. 3,131,509 and 3,564,768. These antagonistic agents have not been notably successful. The aforementioned patent specifically exemplifies the treatment of seeds employing compounds of a different chemical class not suggestive of the present invention.

Other herbicidal compounds whose effect can be modified by the instant compounds include the acetanilides, such as 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide and the urea-type herbicides, such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

It has been discovered that plants can be protected against injury by thiocarbamate-type herbicides, alone or mixed with other herbicides. An alternative mode of action is for the tolerance of the plants to the active herbicidal compounds to be substantially increased by adding to the soil an antidotally effective amount of a compound described in this invention according to the formula ##STR9## in which X, R, R₁, R₂, R₃, R₄, R₅ and R₆ are as defined above.

As an alternative mode of action, the compounds of this invention may interfere with the normal herbicidal action of the thiocarbamate herbicides to render them selective in their action.

Whichever mode of action is operative, the corresponding beneficial and desirable effect is the continued herbicidal effect of the thiocarbamate with the accompanying decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter.

Therefore, the terms herbicide, antidote or antidotal amount, is meant to describe that effect which tends to counteract the normal injurious herbicidal response that the herbicide might otherwise produce. Whether it is to be termed a remedy, interferant, protectant, or the like, will depend upon the exact mode of action. The mode of action is varied, but the effect, which is desirable, is the result of the method of treating the soil in which a crop is planted. Hitherto, there have been no systems which have been satisfactory for this purpose.

The compounds of this invention represented by the above formula can be prepared by several different procedures depending upon the starting materials.

The oxazolidine and thiazolidine intermediates are prepared by the condensation of an amino alcohol or mercaptan with a suitable aldehyde or ketone in boiling benzene with the continuous separation of water. This method is described by Bergmann et al., JACS 75 358 (1953). Usually, the oxazolidines and thiazolidines intermediates are pure enough to be used directly without further purification. Aliquots of these solutions are then used to prepare the compounds of this invention.

The appropriate intermediate is reacted with an acid chloride in the presence of a hydrogen chloride acceptor, such as triethylamine, to prepare the desired compound. Workup and purification procedures involve standard methods of extraction, distillation or crystallization.

The compounds of the present invention and their preparation are more particularly illustrated by the following examples. Following the examples of preparation is a table of compounds which are prepared according to the procedures described herein. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

EXAMPLE I Preparation of 2,2-dimethyl-3-dichloroacetyl oxazolidine.

Five and one-tenth (5.1 g.) grams of 2,2-dimethyl oxazolidine dissolved in 50 ml. of benzene was treated with 5.5 g of triethylamine and 7.4 g. of dichloroacetyl chloride was added dropwise with stirring and cooling in an ice bath. The mixture was poured into water, the benzene solution separated, dried over anhydrous magnesium sulfate and the solvent stripped under vacuum. The product was a waxy solid which had a melting point of 113°-115° C. on recrystallization from diethyl ether.

EXAMPLE II Preparation of 2,2,5-trimethyl-3-dichloroacetyl oxazolidine.

Eighteen (18) milliliters of a benzene solution containing 4.6 g. of 2,2,5-trimethyl oxazolidine was added to 25 ml. of benzene and 4.5 g. of triethylamine. Five and nine-tenths (5.9 g.) grams of dichloroacetyl chloride was added dropwise with stirring and cooling in an ice bath. When reaction was complete the mixture was poured into water and the benzene layer separated, dried over anhydrous magnesium sulfate and the benzene removed under vacuum. Yield was 7.7 g. of an oil, n_(D) ³⁰ =1.4950.

EXAMPLE III Preparation of 2,2-dimethyl-3-dichloroacetyl thiazolidine.

Four and seven-tenths (4.7 g.) grams of 2,2-dimethyl thiazolidine and 4.5 g. of triethylamine were dissolved in 50 ml. of methylene chloride and 5.9 g. of dichloroacetyl chloride was added dropwise with stirring. The mixture was cooled in a water bath at room temperature.

When reaction was complete, the mixture was poured into water and the solvent layer separated, dried over anhydrous magnesium sulfate, and the solvent removed under vacuum. Yield was 3.6 g. of a waxy solid. Recrystallization of another sample from diethyl ether gave a white solid, m.p. 109°-111° C.

EXAMPLE IV Preparation of 2,2,5-trimethyl-3(2',3'-dibromopropionyl)oxazolidine.

Fourteen (14 ml.) milliliters of a benzene solution containing 3.5 g. of 2,2,5-trimethyl oxazolidine was added to 25 ml. of benzene and 3.5 g. of triethylamine. Seven and one-half (7.5 g.) grams of 2,3-dibromopropionyl chloride was added dropwise with stirring and cooling in an ice bath. When reaction was complete, the mixture was poured into water and the benzene layer separated, dried over anhydrous magnesium sulfate and the solvent stripped under vacuum. The yield was 5.7 g. of an oil, n_(D) ³⁰ =1.5060.

EXAMPLE V Preparation of 2,2-dimethyl-3-dibromoacetyl thiazolidine.

To a mixture of 3.5 g. of 2,2-dimethyl thiazolidine, 50 ml. of benzene and 7.1 g. of dibromoacetyl chloride mixed in ice bath was added 3.1 g. of triethylamine dropwise with stirring and continued cooling. When reaction was complete, the mixture was poured into water and the benzene layer separated, dried over magnesium sulfate and the benzene removed under vacuum. Yield was 8.5 g. of a dark oil.

EXAMPLE VI Preparation of 2-ethyl-3-S-ethylthiocarbonyl oxazolidine.

Sixteen and one-half (16.5 ml.) milliliters of a benzene solution of 2-ethyl oxazolidine was added to 50 ml. of benzene and 4.1 g. of triethylamine. Five (5 g.) grams of ethyl chlorothiolformate was added dropwise with stirring and cooling in an ice bath. The mixture was poured into water and the benzene solution separated, dried over anhydrous magnesium sulfate and the benzene stripped under vacuum. Yield was 5.6 g. of an oil, n_(D) ³⁰ =1.5130.

EXAMPLE VII Preparation of 2,2-dimethyl-3-heptanoyl oxazolidine.

Sixteen and one-half (16.5 ml.) milliliters of a benzene solution containing 4.6 g. of 2,2-dimethyl oxazolidine was added to 50 ml. of benzene and 4.1 g. of triethylamine. To this mixture 6 g. of n-heptanoyl chloride was added dropwise with stirring and cooling in an ice bath. The mixture was poured into water and the benzene layer extracted, dried over magnesium sulfate and the benzene removed under vacuum. Yield was 7.5 g. of an oil, n_(D) ³⁰ =1.4598.

                                      TABLE I                                      __________________________________________________________________________      ##STR10##                                                                     COMPOUND                                    m.p. °C.                    NUMBER  R        R.sub.1                                                                              R.sub.2                                                                            R.sub.3                                                                            R.sub.4                                                                             R.sub.5                                                                            R.sub.6                                                                          X or n.sub.D.sup.30                  __________________________________________________________________________     1       CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 116-118                            2       CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.4932                             3       CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.5560                             4       CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O Glass                              5       CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O 1.4842                             6       CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O 1.4950                             7       CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub. 5                                                                   H    H   H O 1.4900                             8       CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    H    H   H O 1.4950                             9       CCl.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    H    H   H O 1.4970                             10      CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    H    H   H O 1.5428                             11      CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O 1.4993                             12      CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    H    H   H O 1.4993                             13      CH.sub.2 Cl                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H O 1.4928                             14      CHCl.sub.2                                                                              CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H O 1.4982                             15      CCl.sub.3                                                                               CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H O 1.5034                             16      CH.sub.3 CHBr                                                                           CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H O 1.5058                             17      CBr.sub.3                                                                               CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H O 95-97                              18      CH.sub.2 Br                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H O 1.5097                             19      CH.sub.2 Br                                                                             CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O 1.5020                             20      CH.sub.2 Br                                                                             CH.sub. 3                                                                            CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    H    H   H O 1.5048                             21      CH.sub.3 (CHBr).sub.4                                                                   CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.5658                             22      CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            H   H O 1.4843                             23      CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            H   H O 120-123                            24      CCl.sub.2                                                                               CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            H   H O 1.5031                             25      CH.sub.2 Br                                                                             CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            H   H O 1.5116                             26      CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            H   H O 1.5140                             27      CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            H   H O 1.5610                             28      ClCH.sub.2 CH.sub.2                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.4538                             29      CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H   H    H   H S 1.5458                             30      CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H S 109-111                            31      CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H O 1.5170                             32      CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O 1.5060                             33      CH.sub.2 BrCHBr                                                                         CH.sub. 3                                                                            CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    H    H   H O 1.5083                             34      CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.5178                             35      CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                  H   H    H   H O 1.5165                             36      CHCl.sub.2                                                                              CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                  H   H    H   H O 1.4949                             37      CBr.sub.3                                                                               CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                  H   H    H   H O 1.5431                             38      CHCl.sub.2                                                                              H     H   CH.sub.3                                                                           CH.sub.3                                                                            H   H O 1.5033                             39      CHCl.sub.2                                                                              CH.sub.3 OCH.sub.2                                                                   H   H   H    H   H O 1.5132                             40      CHCl.sub.2                                                                              C.sub.3 H.sub.7                                                                      H   H   H    H   H O 1.4988                             41      CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H   H    H   H O 1.5126                             42      CHBr.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H   H    H   H O 1.5750                             43      CBr.sub.3                                                                               C.sub.2 H.sub.5                                                                      H   H   H    H   H O 1.5610                             44      CH.sub.2 Br                                                                             C.sub.2 H.sub.5                                                                      H   H   H    H   H O 1.5200                             45      CH.sub.3 CHBr                                                                           C.sub.2 H.sub.5                                                                      H   H   H    H   H O 1.5140                             46      (CH.sub.3).sub.2 CBr                                                                    C.sub.2 H.sub.5                                                                      H   H   H    H   H O 1.4958                             47      CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H   H   H    H   H O 1.5273                             48      CH.sub.2 Cl                                                                             C.sub.2 H.sub.5                                                                      H   H   H    H   H O 1.5020                             49      CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H   H    CH.sub.3                                                                           H O 1.4955                             50      CH.sub.2 Cl                                                                             C.sub.2 H.sub.5                                                                      H   H   H    CH.sub.3                                                                           H O 1.4890                             51      CH.sub.2 Br                                                                             C.sub.2 H.sub.5                                                                      H   H   H    CH.sub.3                                                                           H O 1.5064                             52      CHBr.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H   H    CH.sub.3                                                                           H O Glass                              53      CBr.sub.3                                                                               C.sub.2 H.sub.5                                                                      H   H   H    CH.sub.3                                                                           H O Glass                              54      CH.sub.3 CHBr                                                                           C.sub.2 H.sub.5                                                                      H   H   H    CH.sub.3                                                                           H O 1.4978                             55      CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H   H   H    CH.sub.3                                                                           H O 1.5138                             56      (CH.sub.3).sub.2 CBr                                                                    C.sub.2 H.sub.5                                                                      H   H   H    CH.sub.3                                                                           H O 1.4851                             57      CHCl.sub.2                                                                              H     H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5030                             58      CHBr.sub.2                                                                              H     H   C.sub.2 H.sub.5                                                                    H    H   H O Dark liquid                        59      CBr.sub.3                                                                               H     H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5531                             60      CH.sub.2 Br                                                                             H     H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5173                             61      CH.sub.3 CHBr                                                                           H     H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5076                             62      (CH.sub.3).sub.2 CBr                                                                    H     H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4852                             63      CH.sub.2 BrCHBr                                                                         H     H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5249                             64      CCl.sub.3                                                                               H     H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5048                             65      CH.sub.2 Cl                                                                             H     H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4998                             66      CHCl.sub.2                                                                              CH.sub.3                                                                             H   H   H    H   H O 1.5112                             67      CCl.sub.3                                                                               CH.sub.3                                                                             H   H   H    H   H O 1.5148                             68      CH.sub.2 Cl                                                                             CH.sub.3                                                                             H   H   H    H   H O 1.5077                             69      CH.sub.2 Br                                                                             CH.sub.3                                                                             H   H   H    H   H O 1.5263                             70      CHBr.sub.2                                                                              CH.sub.3                                                                             H   H   H    H   H O 1.5471                             71      CBr.sub.3                                                                               CH.sub.3                                                                             H   H   H    H   H O Dark liquid                        72      CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             H   H   H    H   H O 1.5280                             73      CH.sub.3 CHBr                                                                           CH.sub.3                                                                             H   H   H    H   H O 1.5162                             74      (CH.sub.3).sub.2 CBr                                                                    CH.sub.3                                                                             H   H   H    H   H O 1.5013                             75      CHCl.sub.2                                                                              CH.sub.3                                                                             H   H   H    CH.sub.3                                                                           H O 1.4983                             76      CCl.sub.3                                                                               CH.sub.3                                                                             H   H   H    CH.sub.3                                                                           H O 1.4990                             77      CH.sub.2 Cl                                                                             CH.sub.3                                                                             H   H   H    CH.sub.3                                                                           H O 1.4958                             78      CHBr.sub.2                                                                              CH.sub.3                                                                             H   H   H    CH.sub.3                                                                           H O Dark liquid                        79      CH.sub.3 CHBr                                                                           CH.sub.3                                                                             H   H   H    CH.sub.3                                                                           H O 1.5083                             80      CHBr.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H   H    H   H S 1.5782                             81      CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H   H   H    H   H S 1.5650                             82      CCl.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H S 1.5638                             83      CHBr.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H S Dark liquid                        84      CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H S 1.5520                             85      CHCl.sub.2                                                                              H     H   H   H    H   H S 75-77                              86      CHCl.sub.2                                                                              CH.sub.3                                                                             i-C.sub.3 H.sub.7                                                                  H   H    H   H O 1.4960                             87      CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 OH                                                                         H   H O 1.4960                             88      CH.sub.2 BrC(CH.sub.3)Br                                                                C.sub.2 H.sub.5                                                                      H   H   H    H   H O 1.5318                             89      CH.sub.2 BrC(CH.sub.3)Br                                                                C.sub.2 H.sub.5                                                                      H   H   H    CH.sub.3                                                                           H 0 1.5225                             90      CH.sub.2 BrC(CH.sub.3)Br                                                                CH.sub.3                                                                             H   H   H    CH.sub.3                                                                           H O 1.5210                             91      CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4947                             92      C.sub.2 H.sub.5 S                                                                       H     H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4998                             93      C.sub.2 H.sub.5 S                                                                       CH.sub.3                                                                             H   H   H    CH.sub.3                                                                           H O 1.4965                             94      C.sub.2 H.sub.5 S                                                                       C.sub.2 H.sub.5                                                                      H   H   H    CH.sub.3                                                                           H O 1.4973                             95      C.sub.2 H.sub.5 S                                                                       C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4928                             96      CCl.sub.3                                                                               C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4937                             97      CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5198                             98      CH.sub.2 BrC(CH.sub.3)Br                                                                C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5202                             99      CH.sub.2 BrCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4920                             100     CHCl.sub.2                                                                              CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4960                             101     C.sub.3 H.sub.7 S                                                                       CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4900                             102     i-C.sub.3 H.sub.7 S                                                                     CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4875                             103     CCl.sub.3                                                                               CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4990                             104     CH.sub.2 Br                                                                             CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5070                             105     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5168                             106     CH.sub.2 BrC(CH.sub.3)Br                                                                CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                    H    H   H O 1.5160                             107     CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4950                             108     C.sub.4 H.sub.9 S                                                                       CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4928                             109     C.sub.4 H.sub.9 S                                                                       C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4880                             110     CH.sub.3 S                                                                              CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                    H    H   H O 1.4980                             111     C.sub.6 H.sub.13                                                                        CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.4598                             112     CH.sub.3 S                                                                              CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    H    H   H O 1.4913                             113     n-C.sub.3 H.sub.7 S                                                                     CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    H    H   H O 1.4858                             114     i-C.sub.3 H.sub.7 S                                                                     CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    H    H   H O 1.4828                             115     CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.4912                             116     CH.sub.2 BrCHBr                                                                         H     H   CH.sub.3                                                                           CH.sub.3                                                                            H   H O 1.5221                             117     CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H S 1.5263                             118     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H S 1.5573                             119     CH.sub.2 BrCH.sub.2                                                                     H     H   CH.sub.3                                                                           CH.sub.3                                                                            H   H O 1.4890                             120     CH.sub.2 Br                                                                             H     H   H   H    H   H S 1.6032                             121     CH.sub.3 CHBr                                                                           H     H   H   H    H   H S 1.5720                             122     CH.sub.2 BrCH.sub.2                                                                     H     H   H   H    H   H S 1.5629                             123     CH.sub.2 BrCHBr                                                                         H     H   H   H    H   H S 1.5742                             124     CH.sub.3 C(CH.sub.3)Br                                                                  H     H   H   H    H   H S 1.5420                             125     CH.sub.2 ClCH.sub. 2                                                                    H     H   H   H    H   H S 1.5475                             126     BrCH.sub.2 (CH.sub.2).sub.8 CH.sub.2                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.4898                             127     ClCH.sub.2 CH.sub.2 CH.sub.2                                                            CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.4880                             128     ClCH.sub.2 CH.sub.2 CH.sub.2                                                            CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H S 1.5183                             129     CH.sub.3 CHClCH.sub.2                                                                   CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.4896                             130     CH.sub.3 CHClCH.sub.2                                                                   CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.5115                             131     CH.sub.3 CHClCH.sub.2                                                                   CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O 1.4701                             132     C.sub.2 H.sub.5 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.5020                             133     C.sub.2 H.sub.5 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H S 1.5288                             134     C.sub.2 H.sub.5 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O 1.4900                             135     C.sub.3 H.sub.7 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.4972                             136     C.sub.3 H.sub.7 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H S 1.5220                             137     C.sub.3 H.sub.7 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O 1.4870                             138     CH.sub.2 ClCH.sub.2 CH.sub.2                                                            CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O 1.4747                             139     CH.sub.2 Br(CH.sub.2).sub.4                                                             CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H O 1.4970                             140     CH.sub.2 Br(CH.sub.2).sub.4                                                             CH.sub.3                                                                             CH.sub.3                                                                           H   H    CH.sub.3                                                                           H O 1.4886                             141     CH.sub.2 Br(CH.sub.2).sub.4                                                             CH.sub.3                                                                             CH.sub.3                                                                           H   H    H   H S 1.5249                             142     CH.sub.2 BrCBr(CH.sub.3)                                                                H     H   H   H    H   H S Semi-solid                         143     CH.sub.2 Cl                                                                             H     H   H   H    H   H S 1.5540                             144     CHCl.sub.2                                                                              CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H S 1.5443                             145     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H S 1.4327                             146     CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H S 1.4293                             147     CH.sub.2 Cl                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H    H   H S 1.5279                             148     CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H    n-C.sub.3 H.sub.7                                                                  H O 1.4604                             149     CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                           H   H    n-C.sub.3 H.sub.7                                                                  H O 1.4532                             __________________________________________________________________________

It is clear that the classes of herbicidal agents described and illustrated herein are characterized as effective herbicides exhibiting such activity. The degree of this herbicidal activity varies among specific compounds and among combinations of specific compounds within the classes. Similarly, the degree of activity to some extent varies among the species of plants to which a specific herbicidal compound or combination may be applied. Thus, selection of a specific herbicidal compound or combination to control undesirable plant species readily may be made. Within the present invention are prevention of injury to a desired crop species in the presence of a specific compound or combination may be achieved. The beneficial plant species which can be protected by this method is not intended to be limited by the specific crops employed in the examples.

The herbicidal compounds employed in the utility of this invention are active herbicides of a general type. That is, the members of the classes are herbicidally effective against a wide range of plant species with no discrimination between desirable and undesirable species. The method of controlling vegetation comprises applying an herbicidally effective amount of the hereindescribed herbicidal compounds to the area or plant locus where control is desired.

An herbicide as used herein means a compound which controls or modifies the growth of vegetation or plants. Such controlling or modifying effects include all deviations from natural development; for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By "plants" it is meant germinant seeds, emerging seedlings, and established vegetation, including the roots and above-ground portions.

The compounds of this invention were employed in effective herbicidal antidote compositions comprising thiocarbamates in combination with antidote compounds described hereinabove. They were tested in the following manner.

CORN SEED TREATMENT TEST

Small flats were filled with Felton loamy sand soil. Soil incorporated herbicides were applied at this time. The soil from each flat was placed into a five-gallon cement mixer where the soil was mixed as the herbicides were applied using a predetermined amount of a stock solution containing 936 mg. of 75.5% active ingredient to 100 ml. of water. One ml. of stock solution was applied to the soil in a volumetric pipet for each pound of herbicide desired. One ml. of stock solution contained 7 mg. of herbicide which equals one pound per acre when applied to the soil in the flats. After the herbicide incorporation, the soil was placed back into the flats.

Flats of herbicide-treated and untreated soil were then ready to be planted. A pint sample of soil was removed from each flat and placed next to each flat for later use in covering up the seeds. The soil was leveled and rows one-half inch deep were made for planting seeds. Alternating rows of treated and untreated crop seeds were sown. In each test, six PAG 344T field corn seeds were planted in each row. Rows were approximately 11/2 inches apart in the flat. Seeds were treated by either (1) placing 50 mg. of the antidote compound with 10 grams of corn seed in a suitable container and shaking them until the seeds were uniformly covered with the compound; or (2) preparing a stock solution by dissolving 50 mg. of the antidote compound in 5 ml. of acetone then using 0.5 ml. of the solution to treat 10 g. of corn seed (0.05% w/w). Antidote compounds were also applied as liquid slurries and powders or dusts. In some cases, acetone was used to dissolve powdered or solid compounds so they could be more effectively applied to the seeds.

After the flats were seeded, they were covered with the one pint of soil which had been removed just prior to planting. Flats were placed on greenhouse benches where temperatures ranged from 70°-90° F. Flats were watered by sprinkling as needed to assure good plant growth. Percent control ratings were taken two, three and four weeks after the treatments were applied.

In each test, the herbicide was applied alone, in combination with the seed protectant, and the seed protectant was applied alone to check for phytotoxicity. The untreated adjacent row was employed to observe any beneficial lateral movement of the antidote compound through the soil. The degree of the effect was noted by comparison with the control. The results of these tests are tabulated in Table II.

                  TABLE II                                                         ______________________________________                                         Per Cent Injury to Corn from EPTC*                                             Seed Treatment Test                                                                         Per Cent Injury, 2 weeks                                                         Treated      Untreated                                          COMPOUND       Seed         Seed                                               NUMBER         (0.05% w/w)  Adjacent Row                                       ______________________________________                                         1**            5            30                                                 2              70           80                                                 3**            40           60                                                 4              10           50                                                 5              30           60                                                 6              0            0                                                  7              40           55                                                 8              0            15                                                 9              10           55                                                 10             20           60                                                 11             30           50                                                 12             10           40                                                 13             50           70                                                 14             0            20                                                 15             20           50                                                 16             10           55                                                 17             30           50                                                 18             20           50                                                 19             40           50                                                 20             20           60                                                 21             50           50                                                 22             60           60                                                 23             50           60                                                 24             20           60                                                 25             20           70                                                 26             20           60                                                 27             20           60                                                 28             60           70                                                 29             0            5                                                  30             20           5                                                  EPTC 6E Untreated Seed                                                                        --           70                                                                                80 (4 wk.)                                      ______________________________________                                          * = Sethyl dipropylthiocarbamate 6E: 6 lb./ A preplant incorporated            ** = Seed treatment 0.01% w/w                                            

With 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide at 2 lb/A. as a seed treatment (0.5%), Compound No. 144 gave 100% protection to sorghum (Milo).

PROCEDURE: MULTICROP ANTIDOTE SCREEN

Plastic flats were filled with Felton loamy sand soil. Since a variety of grass and broadleaf crops were used in these tests, EPTAM® (EPTC) was incorporated at 1/2 and 5 lb/A, while a constant rate of 5 lb/A of the additive was used. EPTAM® (EPTC) and the herbicide additive were applied separately by pipetting measured amounts of the appropriate stock solutions into the soil during incorporation in a 5 gallon rotary cement mixer. Stock solutions for EPTAM were prepared as follows:

A. 1/2 lb/A: 670 mg. of EPTC 6E (75.5% a.i.) was diluted with 500 ml. of deionized water so that 2 ml. equals 1/2 lb/A/plastic flat.

B. 5 lb/A: 6700 mg. of EPTC 6E (75.5%) was diluted with 500 ml. of deionized water so that 2 ml. equals 5 lb/A/plastic flat.

Additive stock solutions were prepared by diluting 102 mg. of technical material with 10 ml. of acetone 1% Tween 20® (polyoxy-ethylene sorbitan monolaurate) so that 2 ml. equals 5 lb/A/flat.

After the soil was treated with both herbicide and additive the soil was transferred from the mixer back into the flat where it was then prepared for seeding. The initial step in preparation was to remove a one pint sample of soil from each flat to be retained and used to cover the seeds after planting. The soil was then leveled and rows one-quarter inch deep were made in each flat. Flats treated with 5 lb/A of EPTAM were seeded to DeKalb XL-44 corn (Zea maize), US H9 sugarbeets (Beta vulgare), small seeded gray striped sunflower (Helianthus annus), Acala cotton (Gossypium hirsutum), Brag soybeans (Glycine max) and oilseed rape (Brassica napus). Flats treated with 1/2 lb/A of EPTAM were seeded to red oats (Avena byzantina), R-10 [sorghum] (Sorgum vulgare), Fremont HRS wheat (Triticum aestivum), giant foxtail (Seteria feberii), Calrose rice (Oryza sativa) and Blue Mariate barley (Hordeum vulgare). Seeds were then covered with the pint soil sample removed prior to seeding.

The flats were then placed on greenhouse benches where temperatures were maintained between 70°-90° F. The soil was watered by sprinkling to assure good plant growth.

Injury ratings were taken 2 and 4 weeks after the treatments were applied. Soil treated with EPTAM alone at 1/2 or 5 lb/A was included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes. The percent protection of various representative crops is reported in Table III. The percent protection is determined by a comparison with flats not treated with the candidate antidote.

                  TABLE III                                                        ______________________________________                                         Multicrop Screen Results                                                       Per Cent Protection                                                            COMPOUND  Rate of                 % Protection                                 NUMBER    EPTC lb/A   Crop        (2 weeks)                                    ______________________________________                                         31        0.5         barley      56                                                                 rice        30                                           32        0.5         barley      56                                                                 rice        30                                                                 corn        100                                          33        0.5         rice        30                                                                 barley      44                                           34        0.5         barley      88                                                     5.0         corn        100                                          35        0.5         barley      44                                                     5.0         corn        100                                          36        5.0         corn        100                                          37        5.0         corn        100                                          38        0.5         barley      88                                                     5.0         corn        100                                                    5.0         sunflower   50                                           39        5.0         corn        100                                                    5.0         sunflower   25                                                     5.0         oilseed rape                                                                               60                                           40        5.0         corn        100                                                    5.0         sunflower   25                                           41        0.5         barley      50                                                     5.0         corn        100 (4 weeks)                                42        5.0         corn        56 (4 weeks)                                 43        5.0         corn        93 (4 weeks)                                 44        5.0         corn        28 (4 weeks)                                 45        0.5         barley      50                                                     5.0         sunflower   81                                           46        0.5         rice        100 (4 weeks)                                47        0.5         rice        100 (4 weeks)                                          0.5         barley      75 (4 weeks)                                           5.0         oilseed rape                                                                               68 (4 weeks)                                 48        0.5         barley      25                                                     5.0         sunflower   67 (4 weeks)                                 49        0.5         sorghum     50                                                     0.5         barley      50                                                     5.0         corn        100 (4 weeks)                                50        5.0         corn        100 (4 weeks)                                51        5.0         corn        42 (4 weeks)                                 52        5.0         corn        100 (4 weeks)                                53        0.5         rice        100 (4 weeks)                                          0.5         barley      50 (4 weeks)                                           5.0         corn        70 (4 weeks)                                 54        0.5         barley      50                                                     5.0         corn        100 (4 weeks)                                55        0.5         wheat       20 (4 weeks)                                           0.5         barley      100 (4 weeks)                                          5.0         corn        93 (4 weeks)                                 56        0.5         sorghum     10 (4 weeks)                                 57        0.5         barley      50                                                     5.0         corn        100 (weeks)                                  58        0.5         rice        100 (4 weeks)                                59        5.0         corn        93 (4 weeks)                                 60        0.5         rice        100 (4 weeks)                                          5.0         corn        42 (4 weeks)                                 61        0.5         sorghum     40 (4 weeks)                                           0.5         barley      75 (4 weeks)                                           5.0         rice        70 (4 weeks)                                 62        5.0         oilseed rape                                                                               65 (4 weeks)                                 63        0.5         barley      75                                           64        5.0         corn        42 (4 weeks)                                 65        5.0         corn        70 (4 weeks)                                 66        5.0         corn        100 (4 weeks)                                67        5.0         corn        28 (4 weeks)                                 68        0.5         rice        100 (4 weeks)                                          5.0         corn        93 (4 weeks)                                 69        5.0         corn        42 (4 weeks)                                 70        5.0         corn        100 (4 weeks)                                71        5.0         corn        70 (4 weeks)                                 72        0.5         rice        100 (4 weeks)                                          0.5         barley      50 (4 weeks)                                           5.0         corn        100 (4 weeks)                                73        5.0         corn        100 (4 weeks)                                74        5.0         corn        42 (4 weeks)                                 75        0.5         sorghum     71                                                     0.5         wheat       60                                                     5.0         corn        87                                                     5.0         oilseed rape                                                                               71                                           76        5.0         corn        56 (4 weeks)                                 77        5.0         corn        100 (4 weeks)                                          5.0         sugarbeets  28 (4 weeks)                                 78        0.5         rice        100 (4 weeks)                                          5.0         corn        100 (4 weeks)                                          5.0         sunflower   81 (4 weeks)                                 79        0.5         barley      50                                                     5.0         corn        100 (4 weeks)                                          5.0         sunflower   67 (4 weeks)                                 80        5.0         corn        70 (4 weeks)                                           5.0         oilseed rape                                                                               56 (4 weeks)                                 81        0.5         barley      50 (4 weeks)                                           5.0         sunflower   67 (4 weeks)                                 82        5.0         corn        56 (4 weeks)                                 83        0.5         rice        100 (4 weeks)                                84        0.5         rice        100 (4 weeks)                                          0.5         barley      50 (4 weeks)                                 85        0.5         rice        100 (4 weeks)                                          0.5         barley      75 (4 weeks)                                           5.0         corn        93 (4 weeks)                                 86        0.5         barley      50 (4 weeks)                                           5.0         corn        100 (4 weeks)                                87        5.0         corn        93 (4 weeks)                                 88        0.5         barley      45                                           89        0.5         wheat       67                                                     5.0         oilseed rape                                                                               75                                           90        0.5         wheat       15                                           91        0.5         sorghum     50                                                     5.0         corn        84                                           92        5.0         oilseed rape                                                                               75                                           93        5.0         oilseed rape                                                                               75                                           94        5.0         oilseed rape                                                                               75                                           95        5.0         oilseed rape                                                                               75                                           96        5.0         corn        80                                           97        0.5         barley      50                                           98        5.0         sunflower   60                                           99        0.5         barley      88                                           100       5.0         corn        100                                          101       5.0         sunflower   100                                          102       5.0         oilseed rape                                                                               50                                           103       0.5         sorghum     30 (4 weeks)                                           5.0         corn        100                                          104       0.5         rice        30 (4 weeks)                                           0.5         sorghum     30 (4 weeks)                                 105       0.5         wheat       30 (4 weeks)                                           0.5         barley      75 (4 weeks)                                 106       5.0         sunflower   20 (4 weeks)                                 107       0.5         wheat       40 (4 weeks)                                           0.5         barley      60 (4 weeks)                                           5.0         corn        100 (4 weeks)                                108       5.0         oilseed rape                                                                               75                                           109       5.0         oilseed rape                                                                               75                                           110       5.0         oilseed rape                                                                               75                                           111       5.0         sunflower   60                                           112       5.0         oilseed rape                                                                               75                                           113       5.0         oilseed rape                                                                               67                                           114       5.0         oilseed rape                                                                               33                                           115       0.5         barley      70 (4 weeks)                                           5.0         corn        10 (4 weeks)                                 116       0.5         barley      58 (4 weeks)                                           5.0         sunflower   60 (4 weeks)                                           5.0         corn        100 (4 weeks)                                117       0.5         barley      58 (4 weeks)                                           5.0         corn        100 (4 weeks)                                118       0.5         barley      58 (4 weeks)                                           5.0         corn        65 (4 weeks)                                 119       0.5         barley      68 (4 weeks)                                           5.0         corn        100 (4 weeks)                                120       5.0         sunflower   30                                           121       0.5         rice        67 (4 weeks)                                           5.0         oilseed rape                                                                               60 (4 weeks)                                 122       0.5         barley      58 (4 weeks)                                           5.0         corn        100 (4 weeks)                                123       0.5         rice        44 (4 weeks)                                 124       0.5         rice        67 (4 weeks)                                           0.5         barley      58 (4 weeks)                                 125       0.5         rice        88 (4 weeks)                                 126       0.5         rice        100                                                    0.5         barley      100                                          127       0.5         rice        78                                                     0.5         barley      64                                           128       0.5         rice        78                                                     0.5         barley      57                                                     5.0         oilseed rape                                                                               60                                           129       0.5         rice        78                                                     0.5         barley      43                                                     5.0         sunflower   100                                          130       0.5         rice        100                                                    0.5         barley      43                                                     5.0         oilseed rape                                                                               40                                                     5.0         soybeans    33                                           131       0.5         barley      43                                                     5.0         sunflower   100                                                    5.0         oilseed rape                                                                               80                                                     5.0         soybeans    47                                           132       0.5         rice        78                                                     0.5         oats        50                                                     0.5         barley      57                                                     5.0         oilseed rape                                                                               100                                                    5.0         corn        58                                           133       0.5         barley      57                                                     0.5         oats        40                                                     5.0         sugarbeets  45                                                     5.0         oilseed rape                                                                               100                                          134       0.5         barley      43                                                     5.0         soybeans    33                                                     5.0         oilseed rape                                                                               80                                           135       0.5         oats        60                                                     5.0         corn        100                                                    5.0         oilseed rape                                                                               100                                          136       0.5         rice        55                                                     0.5         barley      57                                                     5.0         corn        100                                                    5.0         oilseed rape                                                                               80                                           137       0.5         barley      43                                                     5.0         sunflower   70                                                     5.0         soybeans    33                                           138       0.5         rice        78                                                     0.5         barley      71                                                     5.0         oilseed rape                                                                               60                                           139       5.0         sunflower   70                                                     5.0         oilseed rape                                                                               60                                           140       5.0         sunflower   100                                                    5.0         oilseed rape                                                                               60                                                     5.0         soybeans    33                                           141       5.0         soybeans    47                                                     5.0         oilseed rape                                                                               60                                           142       0.5         rice        86                                                     0.5         barley      62.5                                         143       0.5         rice        100                                                    0.5         barley      87.5                                         144       0.5         sorghum     100                                                    0.5         rice        86                                                     0.5         barley      100                                                    5.0         corn        100                                          145       0.5         rice        100                                                    0.5         barley      100                                          146       0.5         barley      75                                                     5.0         oilseed rape                                                                               100                                          147       0.5         rice        72                                                     5.0         corn        88                                           148*      1.0         sorghum     80 (4 weeks)                                           5.0         corn        100 (4 weeks)                                149*      5.0         corn        100 (4 weeks)                                ______________________________________                                          *Herbicide used VERNAM® (Spropyl N,Ndipropylthiocarbamate). Infurrow       method of application employed to apply antidote compound. Stock solution      used:                                                                          1 lb/A: 633 mg. of VERNAM® (75% a.i.) was diluted with 500 ml. of          deionized water so that 4 ml. applied is equivalent to 1 lb/A per flat.        5 lb/A: 633 mg. of VERNAM® (75% a.i.) was diluted with 100 ml. of          deionized water so that 4 ml. is equivalent to 5 lb/A per flat.          

When used with 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide at 2 lb/A, Compounds No. 1 and 30 at 5 lb/A after 4 weeks gave 100 percent protection to sorghum. Compound No. 1 also gave 67 percent protection to wheat.

When used with 3-(3,4-dichlorophenyl)-1,1-dimethylurea at 1 lb/A, Compounds No. 1 and 30 at 5 lb/A each gave 60 percent protection to cotton; Compound No. 1 also gave 60 percent protection to corn; and Compound No. 30 gave 43 percent protection to corn.

The antidote compounds and compositions of the present invention can be used in any convenient form. Thus, the antidote compounds can be formulated into emulsifiable liquids, emulsifiable concentrates, liquid, wettable powder, powders, granular or any other convenient form. In its preferred form, a non-phytotoxic quantity of an herbicidal antidote compound is admixed with a selected herbicide and incorporated into the soil prior to or after planting the seed. It is to be understood, however, that the herbicides can be incorporated into the soil and thereafter the antidote compound can be incorporated into the soil. Moreover, the crop seed itself can be treated with a non-phytotoxic quantity of the compound and planted into the soil which has been treated with herbicides, or untreated with the herbicide and subsequently treated with the herbicide. The addition of the antidote compound does not affect the herbicidal activity of the herbicides.

The amount of antidote compound present can range between about 0.001 to about 30 parts by weight of antidote compound described herein per each part by weight of herbicide. The exact amount of antidote compound will usually be determined on economic ratios for the most effective amount usable. It is understood that a non-phytotoxic quantity of antidote compound will be employed in the herbicidal compositions described herein. 

What is claimed:
 1. A compound having the formula ##STR11## in which R is haloalkyl having from 1 to 10 carbon atoms, inclusive, halo is selected from chloro and bromo, R₃ is lower alkyl having from 1 to 4 carbon atoms, inclusive, and R₁, R₂, R₄, R₅ and R₆ are each hydrogen. 